Treatment of fibres

ABSTRACT

Wool is rendered resistant to shrinkage on washing by treatment with from 0.1 to 10% by weight of a composition obtained by mixing (A) a polydiorganosiloxane having terminal silicon-bonded hydroxyl radicals and (B) an organosilane RSiR&#39;&#39;.sub.n X.sub.3-n, in which R is a monovalent radical containing at least two amine groups, R&#39;&#39; is alkyl or aryl, X is alkoxy and n is 0 or 1, and/or a partial hydrolysate and condensate of the silane. The applied composition is thereafter cured.

United States Patent 11 1 1111 3,876,459 Burrill 5] Apr. 8, 1975 [54]TREATMENT OF FTBRES FOREIGN PATENTS 0R APPLICATIONS [75] Inventor: PeterMartin Burrill, Glamorgan, 594901 11/1947 United Kingdom Wales 746,3073/1956 United Kingdom [73] Assignee: Dow Corning Limited, London,

England Primary Examiner-William. E. Schulz Attorney, Agent, orFirmRobert F. Fleming, Jr. [22] Flled: June 29, 1973 [2]] Appl. No.:374,848 [57] ABSTRACT Wool is rendered resistant to shrinkage on washingby [52] US. Cl. 117/141; 8/l27.6; 8/128 treatment with from 0.1 to l07cby weight ofa compo- [51] Int. Cl C08h 19/04 sition obtained by mixing(A) a polydiorganosiloxane [58] ield O Searc /12 128 ll7/l havingterminal silicon-bonded hydroxyl radicals and 260/465 E (B) anorganosilane RSiR,,X in which R is a monovalent radical containing atleast two amine groups. R [56] References Cited is alkyl or aryl, X isalkoxy and n is 0 0r 1, and/or a UNITED STATES PATENTS partialhydrolysate and condensate of the silane. The 3,247,281 4/1966 Gagliardi117/141 x applied compos'ton hereafter cured- 3,668,00l 6/1972 Hosokawaet al. 117 141 x D 3,705,823 12/1972 Hosokawa et al. 117/141 x 6 N0rawmgs TREATMENT or FIBRES This invention relates to a process for thetreatment of keratinous fibres.

It has been proposed to reduce the shrinkage of wool on washing bytreatment with various organosilicon compounds. For example in U.K. Pat.Nos. 594,901, 613,267 and 629,329 it is proposed to reduce the normaltendency of wool to shrink by treating the wool with certain alkyl oraryl silanes. In UK. Pat. No. 746,307 there is disclosed a process forpreventing the shrinkage of wool by treating the wool with a compositionconsisting of a diorganopolysiloxane, in which the organic substituentsare alkyl, phenyl or alkenyl, and a siloxane containing silicon-bondedhydrogen atoms.

While the known processes have conferred a degree of shrink resistanceon woollen fabrics this effect has not been durable to laundering. Therehas consequently been a need for a shrink resistant treatment havingimproved durability to washing and which imparts to the fibres a durablesoft handle.

We have now discovered that the above recited advantages of durabilityof handle and shrink resistance may be realised by treatment ofkeratinous fibres with certain siloxane compositions.

According to this invention there is provided a process for thetreatment of keratinous fibres which comprises applying thereto from 0.1to 10% by weight, based on the weight of the fibres, of a compositioncomprising the product obtained by mixing (A) a polydiorganosiloxanehaving terminal silicon-bonded hydroxyl radicals and a molecular weightof at least 750, at least 50 percent of the organic substituents in thepolydiorganosiloxane being methyl radicals, any other substituents beingmonovalent hydrocarbon radicals having from 2 to carbon atoms and (B) anorganosilane of the general formula RSiR' X wherein R represents amonovalent radical composed of carbon, hydrogen, nitrogen and,optionally, oxygen, which radical contains at least two amine groups andis attached to silicon through a silicon to carbon linkage, R'represents an alkyl radical or an aryl radical, each X represents analkoxy radical having from 1 to 14 inclusive carbon atoms and n is 0 or1, and/or a partial hydrolysate and condensate of said organosilane, andthereafter curing the applied composition.

The invention also includes keratinous fibres whenever treated by thesaid process.

The polydiorganosiloxanes (A) are linear or substantially linearsiloxane polymers having terminal siliconbonded hydroxyl radicals. Suchpolydiorganosiloxanes have about two, that is from about 1.9 to 2,organic radicals per silicon atom and methods for their preparation arewell known in the art. The polydiorganosiloxanes should have an averagemolecular weight of at least 750 and preferably from 20,000 to 90,000.

At least 50 percent of the silicon-bonded organic substituents in thepolydiorganosiloxane are methyl, any other substituents being monovalenthydrocarbon radicals having from 2 to 30 carbon atoms, for example alkyland cycloalkyl radicals, e.g. ethyl, propyl, butyl, n-octyl, tetradecyl,octadecyl and cyclohexyl, alkenyl radicals e.g. vinyl and allyl andaryl, aralkyl and alkaryl radicals e.g. phenyl, tolyl and benzyl. Asmall proportion of hydroxyl radicals may be attached to nonterminalsilicon atoms in the polydiorganosiloxane.

However, such non-terminal hydroxyl radicals should preferably notexceed about 5% of the total substitu ents in the polydiorganosiloxane.The preferred polydiorganosiloxanes are the polydimethylsiloxanes i.e.those represented by the formula HO S10 in which a is an integerpreferably having a value such that the polydiorganosiloxane has aviscosity of from to 50,000 cS at 25C.

Component (B) of the compositions employed in the process of thisinvention is an organosilane of the general formula RSiR X wherein R, R,X and n are as defined hereinabove or may be a partial hydrolysate andcondensate of said organosilane. Such organosilanes are known substancesand they may be prepared as described, for example, in U.K. Pat. Nos.858,445 and 1,017,257. In the general formula of the organosilanes theradical R is composed of carbon, hydrogen, nitrogen and, optionally,oxygen and contains at least two amine (which term includes imine)groups. It is attached to silicon through a silicon to carbon linkage,there being preferably a bridge of at least 3 carbon atoms separatingthe silicon atom and the nearest nitrogen atom or atoms. Preferablyalso, R contains less than about 21 carbon atoms and any oxygen ispresent in carbonyl and/or ether groups. Examples of the operative Rsubstituents are (Cl-I NHCH CH NH (CH NHCH CH NHCH CH .CH.CH CH NHCH CHNH (CH NHCH CH NHCH CH NH and (Cl-l Nl-l(CH NHCH CH COOCH Each of the Xsubstituents may be an alkoxy radical having from 1 to 14 carbon atoms,preferably from 1 to 4 carbon atoms. Examples of X radicals are methoxy,isopropoxy, hexoxy and decyloxy. When present R may be any alkyl or arylradical, preferably having less than 19 carbon atoms, e.g. methyl,ethyl, propyl, octyl or phenyl. Preferred as component (B) are theorganosilanes having the general formula RSiX wherein R represents the(CH NHCH Cl-l Nl-l or the Cl-l CHCH Cl-l NHCH CH Nl-l radicals and eachX represents the methoxy or ethoxy radicals.

In the practice of this invention the product obtained by mixingcomponents (A) and (B) is applied to keratinous fibres. When components(A) and (B) are mixed together at normal or elevated temperatures theyreact, at least partially. The product applied to the fibres willtherefore usually comprise, at least in part, a reaction product of (A)and (B) rather than a simple mixture of these two. The composition maybe applied to the keratinous fibres using any suitable applicationtechnique, for example by padding or spraying. Most conveniently thecomposition is applied in the form of a dispersion or solution in aliquid carrier. Preferably the compositions are applied as a solution inan organic solvent. Solvents which may be employed include thehydrocarbons and chlorinated hydrocarbons, for example toluene, xylene,white spirit and perchloroethylene. A particularly convenient method oftreating the fibres is by application from an organic solvent solutionemploying a conventional dry-cleaning machine. When application from anaqueous medium is desired it is preferred to employ as component (B)organosilanes in which X contains 3 or more carbon atoms and topartially react (B) with (A), or with both (A) and (C), prior toemulsification.

The relative proportions of (A) and (B) employed in the preparation ofthe mixture may vary between fairly wide limits. Preferably from 0.5 toparts by weight of the silane (B) are employed per 100 parts by weightof (A), but proportions of (B) in excess of 15 parts, for example up to50 parts or more are operative.

Following application of the composition the treated fibres are driedand the deposited composition cured. Drying and curing may be carriedout by merely exposing the treated fibres to normal atmospherictemperatures (about C) for periods of from several hours to severaldays. If desired, however, this step may be expedited by the use ofelevated temperatures, e.g. from 60 140C. Curing is believed to beinitiated by traces of water. Under normal conditions the moisturepresent in the atmosphere and/or in the applied composition issufficient for this purpose. If necessary, however, the water content ofthe curing environment may be supplemented.

According to a further aspect of this invention we have found that thetime and/or temperature required for cure of the applied composition maybe significantly reduced if there is incorporated in the appliedcomposition certain silanes or partial hydrolysates thereof. In apreferred method of carrying out this invention therefore thecomposition applied to the fibres has incorporated therein a thirdcomponent (C) which is (i) a silane of the formula R",,,SiZ where R" isa hydrogen atom or a monovalent hydrocarbon radical or monovalenthalogenated hydrocarbon radical, Z is an alkoxy or alkoxy alkoxy radicalhaving from 1 4 inclusive carbon atoms and m is 0 or 1 and/or (ii) apartial hydrolysate and condensate of the said silane. Compositionscomprising (A), (B) and (C) are novel and are included within the scopeof this invention.

In the general formula of the silane (i) R may be hydrogen atom or amonovalent hydrocarbon radical or halogenated hydrocarbon radical, forexample alkyl, e.g. methyl, ethyl, propyl, butyl, hexyl, decyl,octadecyl, alkenyl e.g. vinyl or allyl, aryl, aralkyl or alkaryl e.g.phenyl, tolyl or benzyl, halogenoalkyl e.g. chloromethyl, bromoethyl 0r3,3,3-trifluoropropyl and halogenoaryl e.g. chlorophenyl. The radical Zmay be for example methoxy, ethoxy, propoxy or methoxyethoxy. PreferablyZ is methoxy or ethoxy and R", when present, is methyl. Examples of thesilanes (i) and their partial hydrolysis and condensation products (ii)are methyltrimethoxysilane, ethyltrimethoxysilane,n-propyltriethoxysilane, phenyltriethoxysilane, tetraethylorthosilicate, n-butyl orthosilicate, ethyl polysilicate and siloxanescontaining both silicon-bonded methyl radicals and methoxy radicals.

Component (C) is best incorporated into the composition by mixing withcomponents (A) and (B) prior to dispersion or solution. The proportionof (C) employed is not narrowly critical. Preferably it is present in aproportion of from 1 to 20 percent by weight based on the total weightof (A) and (B).

Use of component (C) expedites curing of the applied composition andenables a more consistent improvement in shrink resistance to beobtained. The ex tent of the advantage obtained will vary somewhatdepending on the nature of (C). As an indication, however, the presenceof methyltrimethoxysilane in the composition enables significant shrinkresistant properties to be obtained after several minutes cure at aboutC or by exposure to normal atmospheric temperatures for a period of from4 to 24 hours.

The time and/or temperature required for curing the applied compositionmay also be reduced by incorporating in the composition a siloxanecondensation catalyst. Such catalysts may be employed in place of or inaddition to the silane component (C). Substances which function assiloxane condensation catalysts are well known in the art. Particularlysuitable catalysts for use in the process of the present invention arethe metal organic compounds, for example, the titanium alkoxides andchelates e.g. tetrabutyl titanate, tetraisopropyl titanate anddi-isopropoxytitanium di(ethylactoacetate), and metal carboxylates e.g.stannous octoate, dibutyltin dilaurate, dibutyltin diacetate and leadoctoate. The catalysts are employed in conventional catalyticproportions, normally from 0.1 to 5% by weight based on the combinedweights of (A) and (B).

The use of siloxane condensation catalysts as described hereinabove can,however, significantly reduce the useful (bath) life of thecompositions. In general therefore, the use of the siloxane condensationcatalyst is less preferred than the incorporation of the silane (C) as ameans of expediting curing.

The process of this invention finds application in the treatment ofkeratinous fibres to endow such fibres with a resistance to shrinkage onwashing and also with a durable soft handle. The fibres may be treatedin any form, any example of yarns, knitted or woven fabrics or made upgarments. They may be present as the sole fibres or as blends with othertypes of fibre. Where improved handle of the treated fibres is theprimary consideration, this may be achieved by depositing on the fabricas little as 0.1% of its weight of the composition. When a significantlevel of shrink resistance is required a somewhat higher level ofapplication of the composition, e.g. from about 0.5 to 10%, preferablyfrom 1 to 5%, is more appropriate. The weight of composition applied tothe fibres, as referred to herein, means the weight of activeingredients namely (A) and (B), or (A), (B) and (C), deposited on thefibres.

If desired the treated fibres may be endowed with a firmer handle byincluding in the applied composition a resinous organosiloxane polymer,for example a resinous copolymer of (CH SiO and SiO groups.

The following examples, in which the parts are expressed by weight,illustrate the invention. The partial condensate of CH Si(OCI-I employedin certain of the examples was prepared by refluxing the silane withaqueous sodium hydroxide solution (0.25% by weight NaOI-I) for 3 hours.The partial condensate was then recovered after neutralisation andremoval of volatiles.

Example 1 A composition was prepared by mixing Polydimethylsiloxanehaving terminal SiOH Three parts by weight of the composition were thendissolved in 97 parts by weight of toluene. This solution was used totreat 3 samples of 1:] cover factor, knitted 228s botany wool fabric bypadding at 100% mangle expression. After treatment the samples wereallowed to air dry at 22C for 1 hour and then placed in an aircirculating oven at 120C for 5 minutes.

A square of cm. side was marked out on each of the treated samplesemploying a template and the samples were then washed in 1.25% by weightphosphate buffer solution (pl-I7) containing 1 g./litre of sodiumdioctyl sulphosucciante. The temperature of the wash water was 40C andwashing was carried out in a domestic automatic washing machine.

After 5 minutes the wash was interrupted and the dimensions of themarked square measured with the fabric in the wet state. The wash wasthen continued for 6 hours after which time the marked square wasmeasured again.

The area felting shrinkage of the samples was then calculated accordingto the formula Area felting shrinkage (P8) width shrinkage (WS) X lengthshrinkage (LS) WS X LS/lOO The width shrinkage and length shrinkage weredetermined according to the formula Width or length shrinkage dimensionafter 5 minutes dimension after 6 hours. The average value of percentagearea felting shrinkage for the 3 samples was 0.2%. The value obtainedwith control samples of untreated wool was 72%.

Example 2 The procedure of Example 1 was repeated except that the fabricsamples were of chlorinated wool and washing of the samples was carriedout in an International Cubex Machine according to the method ofInternational Wool Secretariat Specification W.S.S. 128, Test Method No.185 (Superwash specification).

In this case the value of area felting shrinkage obtained was 3.3%.

Example 3 Four compositions, designated A to D, were prepared by mixing:

Pol dimethylsiloxane as employed in xample 1 x parts X Si(CH NHCH,CH NHy parts Partial condensate of CH Si(OCH;,) '1. parts The values X x, yand z in the composition were as follows:

Three parts of each of the compositions was then dissolved in 97 partsof perchloroethylene and the compositions employed to treat samples ofknitted botany wool fabric (228s, l:l cover factor) by padding at 100%mangle expression. After treatment the samples were allowed to dry andcure at 25C for 24 hours.

On completion of the 24 hour curing period the shrinkresist propertiesof the wool samples following washing were measured according to theprocedure employed in Example 2. In each case the area felting shrinkagewas less than 10%.

Example 4 The procedure of Example 1 was repeated except that the methyltrimethoxysilane component was omitted from the composition and theaminosilane was employed at a level of 10 parts per parts ofpolydimethylsiloxane. Cure of the applied composition in this case wasbrought about by exposing the treated fabric to a temperature of about25C for 4 days.

The area felting shrinkage for the treated fabrics was measuredaccording to the procedure of Example 2 and a value of 14% obtained.

Example 5 A composition was prepared by mixing:

Polydimethylsiloxane having terminal i SiOH 88.2 parts groups and M.Wt.60.000

Partial condensate of CH;.Si(OCH 1.8 parts Three parts of thecomposition were dissolved in perchloroethylene (97 parts) and thesolution applied to samples of knitted botany wool (228s, 1:1 coverfactor) by padding at 100% mangle expression. The samples were thenexposed to the air at 25C for 24 hours and the area felting shrinkagemeasured after washing according to Example 2. A value of 5% wasobtained.

Example 6 Three compositions were prepared according to the followingformulation Polydimethylsiloxanc of Example 1 88.2 parts (CH O -,Si(CH,NHCH CH N H 10 parts Silicate 1 .8 parts Example 7 The procedure ofExample 1 was repeated except that the composition was prepared bymixing,

Polydimethylsiloxane as Example 1 (CH O) CH Si(CH )=.NHCI-I CH NH 5parts parts The washing period was 3 hours, and curing was carried outfor 30 minutes at 120C. The area felting shrinkage of the treatedsamples after washing'was 1%.

Example 8 Compositions were prepared by mixing,

Polydimethylsiloxane used in Example 1 Partial. condensate of CHSi(OC1-1 The compositions were applied to samples of botany wool bypadding from 3% solutions in perchloroethylene. The samples were thendried by exposure to the ambient atmosphere (21C) for 4 hours.Measurement of the area felting shrinkage according to the procedure ofExample 2 gave a value of 3.6% for the composition containing silane(a), 1.3% for (b) and 14.1% for (c).

That which is claimed is:

l. A process for the treatment of keratinous fibres which comprisesapplying thereto from 0.1 to 10% by weight, based on the weight of thefibres, ofa composition comprising the product obtained by mixing (A) apolydiorganosiloxane having terminal silicon-bonded hydroxyl radicalsand a molecular weight of at least 750, at least 50 percent of theorganic substituents present in the polydiorganosiloxane being methylradicals, any other radicals being monovalent hydrocarbon radicalshaving from 2 to 30 carbon atoms, (B) up to 50 parts by weight per 100parts (A) of an organosilicon compound selected from the groupconsisting of organosilanes of the general formula RSiR,,X wherein Rrepresents a monovalent radical of less than 21 carbon atoms composed ofcarbon, hydrogen, nitrogen and, optionally, oxygen, which radicalcontains at least two amine groups and is attached to silicon through asilicon to carbon linkage, R represents a radical having less than 19carbon atoms selected from the group consisting of alkyl radicals andaryl radicals, each X represents an alkoxy radical having from 1 to 14inclusive carbon atoms and n is O or 1, and partial hydrolysate andcondensate products of said organosilanes, and (C) in amount from thatsufficient to significantly reduce the time and temperature required tocure the composition to 20 parts based on the weight of (A) and (B) ofan organosilicon compound selected from the group consisting of (i)silanes of the general formula R",,,SiZ wherein R" represents asubstituent selected from the group consisting of hydrogen atoms,monovalent hydrocarbon radicals having from 1 to 18 carbon atoms andmonovalent halogenated hydrocarbon radicals having from 1 to 18 carbonatoms, Z represents a radical selected from the group consisting ofalkoxy radicals and alkoxyalkoxy radicals having from 1 to 4 inclusivecarbon atoms and m is or 1, and (ii) partial hydrolysates andcondensates of (i), and

thereafter curing the applied composition.

2. A process as claimed in claim 1 wherein (C) is employed in aproportion of from 1 to 20 percent by weight based on the total weightof (A) and (B).

3. A process as claimed in claim 1 wherein (B) is an organosilane havingthe general formula RSiX in which R is selected from the groupconsisting of 88.2 parts parts 1 -8 Parts (CH NHCH CH NH and CH CHCH CHNHCH CH NH radicals and each X is selected from the group consisting ofmethoxy and ethoxy radicals.

4. A process as claimed in claim 3 wherein the composition is applied tothe fibres as a solution in an organic solvent.

5. A composition comprising the product obtained by mixing (A) apolydiorganosiloxane having terminal silicon-bonded hydroxyl radicalsand a molecular weight of at least 750, at least 50 percent of theorganic substituents in the polydiorganosiloxane being methyl radicals,any other substituents being monovalent hydrocarbon radicals having from2 to 30 carbon atoms, (B) an organosilicon compound selected from thegroup consisting of organosilanes of the general formula RSiR' X whereinR represents a monovalent radical composed of carbon, hydrogen, nitrogenand, optionally, oxygen, which radical contains at least two aminegroups and is attached to silicon through a silicon to carbon linkage, Rrepresents a radical having less than 19 carbon atoms selected from thegroup consisting of alkyl radicals and aryl radicals, each X representsan alkoxy radical having from 1 to 14 inclusive carbon atoms and n is 0or 1, and partial hydrolysate and condensate products of saidorganosilanes, and (C) an organosilicon compound selected from the groupconsisting of (i) silanes of the general formula R",,,SiZ m wherein R"represents a substituent selected from the group consisting of hydrogenatoms, monovalent hydrocarbon radicals having from 1 to 18 carbon atomsand monovalent halogenated hydrocarbon radicals having from 1 to 18carbon atoms, Z represents a radical selected from the group consistingof alkoxy radicals and alkoxyalkoxy radicals having from 1 to 4inclusive carbon atoms and m is 0 or 1, and (ii) partial hydrolysatesand condensates of (i) wherein component (B) is employed in a proportionof from 0.5 to 15 percent by weight based on the weight of (A) andcomponent (C) is employed in a proportion of from 1 to 20 percent byweight based on the total weight of (A) and (B).

6. A composition as claimed in claim 5 which also comprises an organicsolvent.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF (IORECTINPATENT NO. 3,876, t59 DATED April 8, 1975 |NVENTOR(S) PETER MARTINBURRILL and CHRISTOPHER MILES BROOKE It is certified that error appearsin the above-identified patent and that said Letters Patent are herebycorrected as shown below:

In the heading, CHRISTOPHER MILES BROOKE-- should be noted as the secondinventor in this patent.

Signed and $ealed this twentieth D 3y Of April 1 9 76 [SEAL] 1 Arrest:

RUTH C. MASON Arresting Officer Disciaimer 3,876,459.Pete1- MartinBarri-Z1, Glamorgan, Vales. TREATMENT OF FIBRES. Patent dated Apr. 8,1975. Disclaimer filed Dec. 8, 1975, by the assignee, Dow OwningLimited. Hereby enters this disclaimer to claims 5 and 6 of said patent.

[Ofiez'al Gazette Febwuowy 10, 1.976.]

1. A PROCESS FOR THE TREATMENT OF KERATINOUS FIBRES WHICH COMPRISESAPPLYING THERETO FROM 0.1 TO 10% BY WEIGHT, BASED ON THE WEIGHT OF THEFIBERS, OF A COMPOSITION COMPRISING THE PRODUCT OBTAINED BY MIXING (A) APOLYDIORGANOSILOXANE HAVING TERMINAL SILICON-BONDED HYDROXYL RADICALSAND MOLECULAR WEIGHT OF AT LEAST 750, AT LEAST 50 PERCENT OF THE ORGANICSUBSTITUENTS PRESENT IN THE POLYDIORGANOSILOXANE BEING METHYL RADICALS,ANY OTHER RADICALS BEING MONOVALENT HYDROCARBON RADICALS HAVING FROM 2TO 30 CARBON ATOMS, ((B) UP TO 50 PARTS BY WEIGHT PER 100 PARTS (A) OFAN ORGANOSILICON COMPOUND SELECTED FROM THE THE GROUP CONSISTING OFORGANOSILANES OF THE GENERAL FORMULA RSIR''NX3-N WHEREIN R REPRESENTS AMONOVALENT RADICAL OF LESS THAN 21 CARBON ATOMS COMPOSED OF CARBON,HYDROGEN, NITROGEN AND, OPTIONALLY, OXYGEN, WHICH RADICAL CONTAINS ATLEAT TWO AMINE GROUPS AND IS ATTACHED TO SILICON THROUGH A SILICON TOCARBON LINKAGE, R'' REPRESENTS A RADICAL HAVING LESS THAN 19 CARBONATOMS SELECTED FROM THE GROUP CONSISTING OF ALKYL RADICALS AND ARYLRADICALS, EACH X REPRESENTS AN ALKOXY RADICAL HAVING FROM 1 TO 14INCLUSIVE CARBON ATOMS AND N IS 0 OR 1, AND PARTIAL HYDROLYSATE ANDCONDENSATE PRODUCTS OF SAID ORGANOSILANES, AND (C) IN AMOUNT FROM THATSUFFICIENT TO SIGNIFICANTLY REDUCE THE TIME AND TEMPERATURE REQUIRED TOCURE THE COMPOSITION TO 20 PARTS BASED ON THE WEIGHT OF (A) AND (B) OFAN ORGANOSILICON COMPOUND SELECTED FROM THE GROUP CONSISTING OF (I)SILANES OF THE GENERAL FORMULA R"MSIZ4-M WHEREIN R" REPRESENTS ASUBSTITUENT SELECTED FROM THE GROUP CONSISTING OF HYDROGEN ATOMS,MONOVALENT HYDROCARBON RADICALS HAVING FROM 1 TO 18 CARBON ATOMS ANDMONOVALENT HALOGEN HYDROCARBON RADICALS HAVING FROM 1 TO 18 CARBONATOMS, Z REPRESENTS A RADICAL SELECTED FROM THE GROUP CONSISTING OFALKOXY RADICALS AND ALKOXYALKOXY RADICALS HAVING FROM 1 TO 4 INCLUSIVECARBON ATOMS AND M IS 0 OR 1, AND (II) PARTIAL HYDROLYSATES ANDCONDENSATES OF (I), AND THEREAFTER CURING THE APPLIED COMPOSITION.
 2. Aprocess as claimed in claim 1 wherein (C) is employed in a proportion offrom 1 to 20 percent by weight based on the total weight of (A) and
 3. Aprocess as claimed in claim 1 wherein (B) is an organosilane having thegeneral formula RSiX.sub.3 in which R is selected from the groupconsisting of --(CH.sub.2).sub.3 NHCH.sub.2 CH.sub.2 NH.sub.2 and--CH.sub.2 CHCH.sub.3 CH.sub.2 NHCH.sub.2 CH.sub.2 NH.sub.2 radicals andeach X is selected from the group consisting of methoxy and ethoxy
 4. Aprocess as claimed in claim 3 wherein the composition is applied to
 5. Acomposition comprising the product obtained by mixing (A) apolydiorganosiloxane having terminal silicon-bonded hydroxyl radicalsand a molecular weight of at least 750, at least 50 percent of theorganic substituents in the polydiorganosiloxane being methyl radicals,any other substituents being monovalent hydrocarbon radicals having from2 to 30 carbon atoms, (B) an organosilicon compound selected from thegroup consisting of organosilanes of the general formula RSiR''.sub.nX.sub.3.sub.-n wherein R represents a monovalent radical composed ofcarbon, hydrogen, nitrogen and, optionally, oxygen, which radicalcontains at least two amine groups and is attached to silicon through asilicon to carbon linkage, R represents a radical having less than 19carbon atoms selected from the group consisting of alkyl radicals andaryl radicals, each X represents an alkoxy radical having from 1 to 14inclusive carbon atoms and n is 0 or 1, and partial hydrolysate andcondensate products of said organosilanes, and (C) an organosiliconcompound selected from the group consisting of (i) silanes of thegeneral formula R".sub.m SiZ.sub. 4.sub.-m wherein R" represents asubstituent selected from the group consisting of hydrogen atoms,monovalent hydrocarbon radicals having from 1 to 18 carbon atoms andmonovalent halogenated hydrocarbon radicals having from 1 to 18 carbonatoms, Z represents a radical selected from the group consisting ofalkoxy radicals and alkoxyalkoxy radicals having from 1 to 4 inclusivecarbon atoms and m is 0 or 1, and (ii) partial hydrolysates andcondensates of (i) wherein component (B) is employed in a proportion offrom 0.5 to 15 percent by weight based on the weight of (A) andcomponent (C) is employed in a proportion of from 1 to 20 percent by 6.A composition as claimed in claim 5 which also comprises an organicsolvent.